Fluorinated elastomer with oxygen in chain



United States Patent ICC 3,391,118

Patented July 2, 1968 3 391 118 sodium salt of Cl(CF CFCl) CF COOH, by decarboxylaa tion under vacuum. In a typical preparation, 267 grams gfgggg fi ggfitz WITH of this sodiunr San Cl(CF CFCl) CF C00Na were Edward W Cook, Princeton, NJ assign to FMC 5 pklaced 1n a 1 liter vacuum flask, whlch was evacuated Corporation, New York, NE. a emporium of t rough a dry ice-cooled trap to about 1 mm. pressure, Delaware and then heated to 150 C. The precursor TCPFH distilled N0 Drawing. Filed May 7, 1965, Ser. No. 454,193 into the trap, was washed with water, aqueous sodi- 3 Claims. (Cl. 260-451) um carbonate, and water again, and dried. Distillation of the crude dried product gave 159 grams of pure TCPFH 10 boiling at 161-162 C.-a 75% yield. Its infrared spec- ABSTRACT OF THE DISCLQSURE trum checked that of known material. Fluorinated elastomers having a polymeric structure of The 4'Ch1otopel'huotoheptadishe-1,6 was P p as alternating diene and diol units are prepared by reacting foilOws! a substantially fluorinated terminal diene with a substana stirred fethlXihg mixture of 16 mole) of tially fluorinated diol free of fluorine substitution on the Zinc dust, 1 g of Zinc Chloride, d 25 ml. of isopropanol hydroxy carbon atoms in the presence of an alkali. was added 111016) Of 4,6,74rich10r0pstflu0r0- l-heptene over a six hour period. After refluxing an additional 0.5 hour, the mixture was filtered from unreacted This invention relates to fluorinated elastomers designed Zinc and h iiitiate diluted h t Hal V lumes of waterto have excellent flexibility at low temperatures. The Organic layer was taken p 111 methylene chloride, I h v di d th t t i l di l hi h are water washed several times, and dried over magnesium pletely or almost completely perfluorinated will react with 'suifate' Distillation gave a of P highly fluorinated terminal dienes in the presence of KOH 9741?} C1761 "D The P y y gas or other alkaline condensing agents, to produce elasto- Chromatography was meric polymers which can be identified by proton nuclear 25 The Product can he further Purified y Iedistiiiatitm, magnetic resonance (NMR) as having a structure in which can be used in crude forms, Using the Crude in Correct diene moieties alternate with diol moieties, the polymers PIOPOItiOH to g the indicated am unt of r a tant. terminating with a group derived either from the diol or The toiiowing expstiment is yp of those Carried from the diene and which are haracterized by extremely out. All are tabulated in the table WhiCh fOHOWS thiS degood low temperature properties. scfiptioh 0f p The diols which can be used include highly fiuroinated T0 11 of the Psfltahediol in 20 e-t e W s added aliphatic alpha-omega diols, either acyclic or cyclic, and Potassium hydfoxide- This IIliXtl1f6 was thell rapidly perfluorinated aromatic diols in which the hydroxyls are Poured into 16 of this heptadiene cohtainsd n E1 250 in th para position so th t they are i ffe t i L ml. Erlenmeyer flask and the resultant mixture stirred In the case of cycloaliphatic diols, the hydroxyls should magheticaliy- The light ysiiow 00101" which m d iIr1- similarly be at opposite ends of the ring. Even in the most medistsiy slowly darkened and, after 72 tail to hYOwIl highly fluorinated diols, the carbon atoms to which the p was found in the hash along With a Viscous hydroxyls are attached Will have no fluorine substituent, The Oil was dissolved in acetone, the solution decanted,

since u h compounds are t bl and the polymer washed 'with acetone. The polymer was The dienes may be any highly fl i t d l h leached with acetone in a Soxhlet extractor overnight and acyclic aliphatic dienes, or cycloaliphatic dienes in which then dried in a vacuum e the double bonds are at opposite d f th i h Using this procedure the yield of elastomer is generally dienes may be perfluorinated, or may contain minor about 20%, while the lower molecular weight oils are bers of other substituents such as hydrogen or chlorine. Obtained in about 50% Y The eisstolhsf has sXtfsmeiY Typical examples f my invention are h given b good low temperature properties. The value of the glass way of illustration and are not to be considered limiting transition PQiht g) pp to hs in the e g b h O of my invention. of C.

TABLE. COPOLYME RIZATION OF i-CHLO ROPE RFL U0 ROTIEPTA'D IENE 1,0 WITH 2,2,3,3,4,4-I-IEXAFLUO ROPEN'XANEDIO L-1,5

1 There are mechanical losses. 3 Constants determined with Diiierentlal Scanning Calorimeter. 3 Lower molecular weight products not extracted from polymer.

Examples 1 to 5.2,2,3,3,4,4-hexafluoropentanediol- Example 6 and 4'ch10mp erfiuoroheptadlenedfi 5.5 g. of the pentanediol of Example 1 was suspended The diol used, a known compound, has recently become in a mixture of 5 ml. of hexane and 5 ml. of benzene, available on the market; the 4-chloroperfluoroheptadiene- /2 g. of KOH was added to the mixture and it was then 1,6 can be prepared from 4,6,7-trichloroperfluoroheptenepoured into 8 g. of the heptadiene contained in the 250 1 by dechlorination with zinc at low temperatures (reflux ml. Erlenmeyer flask and the resultant mixture was stirred in isopropanol or tetrahydrofuran). for several weeks at reflux. The resultant polymer was The precursor 4,6,7 trichloroperfluoroheptene 1 separated from the solvent, washed with solvent in a (TCPFH) can be prepared in known manner from the Soxhlet extractor overnight and dried. 10.7 g. of polymer 3 was obtained with a T of 54 C. This indicates that prolonged reaction time increases polymer yield substantially.

Example 7 Example 1 was repeated, but the reaction, instead of being run at room temperature, was run at reflux (ca. 60 C.) for 20 minutes. Polymer yield was 9.3 g.

Example 8 Example 1 was repeated, except polymerization was allowed to continue for 24 days. Yield was 24 g.

All of the polymers of Examples 1 to 8 were demonstrated, by proton nuclear magnetic resonance (NMR), to have the structure The presence of fluorine on both sides of the ether linkages makes the polymer highly resistant to hydrolysis.

Example 9 In like manner to Example 1, 18 parts tetrafluorohydroquinone, 16 parts hexafluoro-1,3-butadiene, and 6 parts potassium hydroxide in 50 parts acetone were stirred in a small glass pressure vessel under autogenous pressure for 3 days at room temperature; 18 parts of elastomeric product were recovered. NMR analysis confirmed a linear alternating structure of the general type shown for Examples 1 to 8.

Example 10 In like manner, 29 parts 2,2,3,4,4,5,5,6,7,7-decafluorooctane-1,8-diol (readily prepared from methanol and perfluorohexadiene by the method of J. D. La Zerte and R. J. Kosher, J. Am. Chem. Soc. 77, 910 (1955)), 21 parts perfiuoropentadiene-1,5 (which was prepared in a manner similar to 4-chloroperfluorohepta-l,7-diene) and 5.6 parts potassium hydroxide in 38 parts acetone gave 14 parts elastomer after 2 days.

4 Example 12 From 24 parts 2,2-3,3-tetrafluorobutane-1,4-diol (prepared by lithium aluminum hydride reduction of perfluorosuccinic acid), 34 parts perfiuorocyclohexadiene-1,3 and 8 parts potassium hydroxide in 50 parts water was obtained 17 parts elastomer after 3 days.

NMR analysis of the products of Examples 10 to 12 confirmed the linear alternating structure typical of the polymers of this invention.

Obviously, the examples can be multiplied indefinitely, without departing from the scope of the invention as defined in the claims.

I claim:

1. The method of making polymers which comprises bringing together a highly fluorinated terminal diol and a highly fluorinated terminal diene in the presence of an alkali and allowing the reaction to proceed until an elastic copolymer is produced.

2. The elastomers obtained by reacting a highly fluorinated terminal diol free of fluorine substitution on the hydroxyl carbon atoms with a highly fluorinated terminal diene in the presence of an alkali.

3. The elastomers of claim 2, in which the diol is an alpha-omega chain compound, and the diene is an alphaomega straight chain diene.

4. The elastomer obtained by reacting 2,2,3,3,4,4-hexafluoropentanediol-1,5 with 4-chloroperfiuoroheptadiene- 1,6 in the presence of an alkali.

5. The elastomer obtained by reacting tetrafluorohydroquinone with hexafiuoro-l,3-butadiene in the presence of an alkali.

6. The elastomer obtained by reacting perfluoro-1,7- octadiene with 2,2,3,3,4,4,5,5-octafiuorohexane-1,6-diol in the presence of an alkali.

7. The elastomer obtained by reacting 2,2,3,4,4,5,5,6,7, 7-decafluorooctane-1,8-diol with perfiuoropentadiene-1,5 in the presence of an alkali.

8. The elastomer obtained by reacting 2,2-3,3-tetrafluorobutane-1,4-diol with perfluorocyclohexadiene-1,3 in the presence of an alkali.

References Cited UNITED STATES PATENTS 3,053,823 9/1962 Brehm et 'al. 260921 WILLIAM H. SHORT, Primary Examiner.

LOUISE P. QUAST, Examiner.

M. GOLDSTEIN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,391,118 July 2, 1968 Edward W. Cook It is certified that error appears in the above identified patent and that said Letters Patent are hereby ccrrected as shown below:

Column 3, line 16, "C15 should read CF Signed and sealed this 17th day of February 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR. 

